TWI313679B - Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit - Google Patents

Abstract

Mixture of oligomeric phenazinium compounds contains phenazinium compound(s) selected from compounds (I) with 2 monomer units (A), which are linked through positions 1-4 or 5-8 and optionally have different substituents, compounds (II) with 3 monomer units of this type and other oligomeric phenazinium compounds, with a total of not less than 80 mole-% (I) and (II). Mixture of oligomeric phenazinium compounds contains phenazinium compound(s) selected from compounds (I) with 2 monomer units of formula (A), optionally with different substituents, compounds (II) with 3 monomer units of this type and other oligomeric phenazinium compounds, with a total of not less than 80 mole-% (I) and (II): N(R5)CC(R4)C(R3) = a group of formula (IIIa) or (IIIb); R1-9 = H, halogen, amino, OH, CN, SCN, SH, COOH, COO-salt, COO-ester, SO3H, SO3-salt, SO3-ester or lower alkyl(hetero)aryl; or R1-4, R6-9 = a single bond connecting individual monomer units; or R2, R3 may = oxo, imino or methylene if (A) contains a (IIIb) unit; NCC(R1)C(R2) = a group of formula (IVa) or (IVb); A- = an acid anion Independent claims are also included for the following: (1) preparation of the mixture; (2) acid copper electroplating bath containing the mixture.

Description

1313679 玖, DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a mixture of an oligomeric phenanthrene cation compound and a process for preparing such a mixture. The invention further relates to an acid bath for electrolytically depositing a copper deposit containing the oligomeric ruthenium cation compound and a method of electrolytically depositing a copper deposit using the acid bath. To produce a decorative surface, the mixture of the present invention can be used as a component in a copper plating bath to more particularly form highly bright and uniform copper deposits. The mixture can in turn be used as a component 10 in a copper plating bath to selectively and completely fill the blind microvias of the printed circuit board with copper. In the fabrication of the integrated circuit, the mixture may further be used as a component in a copper plating bath to deposit copper onto the surface of the semiconductor substrate provided with grooves (grooves and vias) for use in The blind microvias are selectively and completely filled into the printed circuit board such that the surface of the 15 semiconductor substrate is completely uniformly coated by copper. I: Prior Art 3 Background of the Invention In order to deposit a bright copper layer instead of a crystalline matte deposit, organic additives are often added to most of the acidic copper bond 20 electrolyte in small amounts. In this method, an additive compound or a compound such as polyethylene glycol, thiourea and its derivatives, ethyl thiourea, thiourethane, and thiosulfate A composition is often used to add. Nowadays, in any case, because of the fact that the quality of the copper plating obtained can not meet the requirements of today's equipment, the additives mentioned are no longer meaningful. The coating thus obtained, if not easily damaged, is 1313679 with poor gloss and insufficient uniformity. Some of the saffron and its derivatives used to make bright copper layers have long been known, as for the saffron used, according to DE-PS 947656 as the only additive, such as dimethyl sulphur azo Alkyl aniline, diethyl 5-based sulphur azobisindenyl aniline, sulphur ash and saffron azophenol. More specifically, the additive can also be used in combination with other additives. DE-AS 1 004 880 implies diethyl indane red azo dimethyl aniline, toluene sulphur azophenol, toluene sulphur azo naphthol or dimethyl benzene sulphur azodiethyl sulfonamide Or it is a phenol red, red toluene, 10 magenta, amethyst, aniline violet, diethyltoluene or dimethyltoluene and thiourea and thiourea derivatives for bright deposition With a uniform copper coating. Japanese Patent Abstract corresponding to JP 60-056086 A relates to a styrene dye and a monosulfide or a disulfide such as 3-sodium-sulfopropyl disulfide and indole-3-sodium-sulfopropyl disulfide. And a combination of polyethers 15 for depositing a highly bright, uniform, ductile copper layer. The implication made in DE-PS 947 656, DE-AS 1 004 880 and the Japanese patent abstract corresponding to JP 60-056086 A is that, in any case, the resulting copper layer has unsatisfactory properties. Further, the use of a thiourea-formaldehyde condensate as an additive for a 20-acid copper plating bath has been described: DE-AS 1 152 863 describes a thiourea-furfural precondensate for use as an acid The only homogeneous agent in the bath to use. The base glossing agent contained in the acid bath is a derivative of dithiocarbamic acid. DE-AS 1 165 962 describes the use of a precondensation product consisting of thiourea, furfural and a compound having at least two NH2 groups in an acid bath 25 for the production of 1313679 uniform copper. coating. The acid bath further contains a base gloss. DE-AS 1 218 247 discloses an acidic electrolytic copper bath for producing a highly bright, uniform copper coating containing a compound which is hardly soluble in water and which is contained in a thiocarbonyl group and an aryl or aromatic group. Intramolecular [at a ratio of 1:1] of the alk 5 group, the two groups are separated by a compound formed by a hetero atom or a ring system bonded to each other. Examples are aromatic N-single substituted products of sulfur semi-condensed diamine urea, further sulfur monocondensed diamine ureas of aromatic aldehydes, derivatives of thiocarbons, derivatives of thiocarboquinone; Thiocarbonyl groups, mono- and 10-poly bis-indenyl carbonyl decylamine, mono- and polysulfuric acid, and quinone dithiocarbammine. These compounds can be used together with an anthracene derivative having the general formula RR'N-CS-S-(CH2)n-SOx-R". Although disclosed in DE-AS 1 152 863, DE-AS 1 165 962 Derivatives of 15 and DE-AS 1 218 247 are also allowed to achieve bright copper surfaces, but because of their poor uniform quality, they are practically unsatisfactory to meet today's needs. Furthermore, with organic sulfur compounds Polyethylene glycol imine is known as: one or several linear or branched 20 polyethylene glycol imines disclosed in DE-AS 1 246 347 or functional derivatives thereof which contribute to the manufacture Bright, uniform and decorative copper coatings are available, and the brightness can be achieved in an extended current density range. These materials can be combined with other current glosses and/or moisturizers. The aerosol is used in an acid bath. 25 Moreover, QE-AS 1 521 062 implies an acid bath composition containing organic sulfides (containing to 1313679 y v' acid groups) which are mixed or chemically Bonded to a polyfluorene comprising at least three, preferably six, oxygen atoms and having a poly The six c_atoms do not have a free aliphatic hydrocarbon chain. These acid baths allow for a deposit of a smooth, bright and ductile copper layer 5. The preferred polyether has a molecular weight of at least 296, more Preferably, it is at least 5000213 dioxolane polymerization product. The phenanthrene dye can also be used in combination with the acid bath additive, such as diethyl phenol and red azobisnonyl aniline, dimethyl phenol. Red azobisnonyl aniline, diethyl phenol and red azophenol, and dimethylazo 10-(2-hydroxyethylamino-5-methyl)-benzene. The phthalocyanine dye allows for high uniformity. With a wide range of bright deposits, it is still not possible to provide a sufficiently high cathode current density for the copper electrolyte described in DE-AS 1 246 347 and DE-AS 1 521 062. After being introduced into an intermediate medium, the copper surface deposited by 15 can only be nickel plated. In addition, U.S. Patent No. 4,551,212 discloses the combination of Yanlu Green B or Yanlu Black R and Tibetan Red T. For depositing copper layers that can be processed in the micrometer range. These copper layers are based on the grain size It is optimized in terms of hardness and hardness. In addition to the above-mentioned command dye, a 20-step humectant and a disodium salt such as bis-(3-thiopropyl disulfide) may be contained in the plating bath. Further, the use of a hydroxylated and halogenated saffron dye has been described in Japanese Patent Abstract corresponding to the JP 60-056086 A patent number. 25 As described in other documents mentioned herein In U.S. Patent No. Q 135371, the patent application specification revision page is 98.03.23 p year} month ten repair 3b 眢 page Τ 351,212 and the corresponding patent number disclosed in the patent number corresponding to jp 60-056086 A patent number. Derivatives only produce the result of poor brilliance and uniformity. DE-AS 20 28 803 and DE-AS 2 039 831 describe the first use of a compound having the following chemical formula <A>: / 〆 6 R8, VR R7

Wherein R, R2, R3, R4, R5, R6, r7, r%r9 are the same or different and are hydrogen, lower alkane, or possibly methyl, ethyl, methoxy or ethoxy substituted The aryl group, and the R5 and R8 systems further represent a single or polymeric sulfonium cation, the A-line is an acid group and the n10 system is an integer from 2 to 100. According to DE-AS 2039831, the starting materials for the preparation of these compounds are monoamines, for example 2-methyl-3-amino-6-didecyl-amino-9-phenyl-phenanthrium Sulfate. Under the use of nitrosylsulfuric acid and nitrous acid, the amine sulfate and sulfuric acid were heavily gasified at _5 °C. After the nitrous acid was destroyed, the reaction solution was heated to 2 ° C. Further, the reaction mixture was neutralized by a test. In principle, it is possible to use these compounds in a copper acid plating electrolyte with a bright and uniform copper layer deposition. In any case, they still lead to very unstable results in copper plating operations. SUMMARY OF THE INVENTION 3 9 1313679 Summary of the Invention Therefore, a basic object of the present invention is to prevent the above disadvantages of the known copper bath. A more particular object of the present invention is to create an additive by which a particularly uniform and glossy, meaning highly bright, and uniform and ductile copper coating is reproducibly manufactured. . It is a further object of the present invention to apply a highly bright, uniform and ductile copper layer to a relatively high current density. Another object of the present invention is to find one of such copper plating baths, i.e., to continuously obtain a copper layer having the desired properties during a long period of plating bath operation. The solution outlined here for the previous problem is to provide a mixture of oligo-fluorene cations as described in the scope of the patent application; the method of claim 15 is to prepare the compound 15 An acid bath for electrolytically depositing a copper deposit, comprising a mixture of the oligomeric phenanthrene cation compounds of the present invention; and the scope of claim 26, as in claim 22; A method of electrolytically depositing a copper deposit using an acid bath containing the mixture. Preferred embodiments of the invention are described in the dependent items. 2) A mixture of oligo-fluorene ruthenium cation compounds in accordance with the present invention may be useful for electrolysis to produce a highly bright, uniform steel deposit for use in the formation of a decorative surface in an acid bath. Furthermore, the mixture can be advantageously used in a copper bath to deposit a steel deposit onto the printed circuit board, allowing the copper deposit to be selectively and completely filled into the printed circuit board. Blind micropores. Moreover, 1, 曰 10 1313679 compound helps to be used in a copper plating bath, and in the manufacture of integrated circuits, a copper deposit is electrolytically deposited to provide grooves (grooves and holes) On the surface of the semiconductor substrate (wafer), in particular, deposited onto a surface having a high aspect ratio groove. Thereby, the copper deposit is uniformly formed on the surface of all five semiconductor substrates.

I: Embodiment: Detailed Description of the Invention The mixture of the oligomeric porphyrin cation compound of the present invention having one of the chemical formulas <1> and <11> is inferred here, The mixture of the oligomeric porphyrin cation compounds in the scope of the patent application is characterized in that it contains at least one of the oligo-phene cation cation compounds mentioned or a mixture thereof The degree of oligomerization is 2 or 3, except for the mixture, which is characterized by a degree of oligomerization of at least 4 for a small amount of higher oligomeric porphyrin cation compound. According to the present invention, higher oligophene cation cation compounds characterized by a degree of oligomerization of at least 4 will be present in the latter mixture in a lesser amount than 20 mol-%. In any event, the mixtures of the invention can be prepared by the process of the invention. In contrast, the mixture of the invention can be achieved by the method described in DE-AS 20 28 803 and DE-AS 20 39 831, the latter method being specially produced in a degree of oligomerization &gt 3 oligophenazine cation compound (having a content of more than 20 mol-%). The term "lower alkyl" as used herein and in the scope of the patent application refers to (31- to C8 alkyl and more preferably (^ to (: 4 alkyl, 11 1313679, Section $2) Modified replacement page means that methyl, ethyl, η-propyl, iso-propyl, η-butyl, iso-butyl and tert-butyl are replaced as described herein and in the scope of the patent application. Alkyl, preferably means sulfo or carboxy substituted alkane 5 as used herein and in the scope of the patent, "aryl" means phenyl or such as naphthyl-1 and naphthyl-2 Polycyclic aromatic, wherein these groups, individually, may be unsubstituted or substituted. If these groups are substituted, they are more particularly alkyl, preferably lower alkyl Substituted by halogen, hydroxyl or amine, wherein the amine group is NH2, NHR 10 or NR'R", wherein R, R' and R" may be lower alkyl, nitrile, thiocyanyl and thio Hydroxy. The phenyl group may be more specifically substituted at the 2-, 4- and 6-positions. As described herein and in the scope of the patent, 'heteroaryl,' preferably α定基, 啥琳基, iso-indolyl. 15 "COO ester," and "so3 ester" as used herein and in the scope of the claims, preferably refers to a carboxylic acid ester such as cooch3, COOC2H5 lower alcohol Etc. 'and sulfuric acid such as S〇3CH3, so3c2h5 lower alcohol, etc. This means a lower alcohol which is a C! to Cs alcohol, preferably a lower alcohol of C] to C4 alcohol, ie methanol , ethanol, η-propanol, isopropanol 20, η-butanol, isobutanol, and tert-butanol. "COO salt" and "SO3 salt" as described herein and in the scope of the patent application, each It refers to a carboxylate and a sulfate, and more particularly, this means a metal salt such as Na+COO or Cu2+(S〇3_)2, a soil metal salt, a salt of a salt, and a copper salt. The dentate described herein and in the scope of the patent application, preferably 12 1313679, means, for example, fluorine, chlorine, bromine, iron, preferably gas. To name the carbon on the backbone of the cation cation monomer unit The purpose of the atom, here and in the scope of the patent application, is based on the IUPAC nomenclature, if the structure shown in this case It can be affirmed that the chemical structure shown in Figure 5 is prioritized. The solution to the preliminary object of the present invention is that a novel mixture of oligophenazine cation compounds can be advantageously used in an acid copper. In the electrolyte, a mixture of the oligomeric porphyrin cation compounds of the present invention can be obtained by using one of the following methods in a "one-pot reaction", a monomeric cation The compound or a mixture of several sulfonium cation compounds is diazotized, and the obtained diazotized compound is reacted by forming a mixture of the oligomeric phenanthrene compounds. In contrast, DE is used. The method described in DE-AS 20 28 803 and DE-AS 15 2039831 does not provide the oligomeric porphyrin cation compounds of the invention. It has been found that the mixtures of the invention can only be prepared using the process of the invention. The oligomeric porphyrin cation compounds in the mixtures of the invention are characterized in that they are dimeric or trimerized, and 20 1. they may more specifically contain one or more hydroxyl groups or better. It is a hydrogen atom, 2. and/or, preferably, not every single monomer has to carry a charge, 13 1313679 3. 彳 / or, the compound in the sub-component may preferably contain different Command the monomer unit. Therefore, a special feature of the present invention is that the mixture of the oligomeric porphyrin cation compounds comprises at least one selected from the group consisting of compounds having two monomer units according to the following Chemical Formula 5 <1:> Command a positive ion compound:

And a compound containing a trimer monomer unit according to the following chemical formula <π>:

(A') (A')

(ΑΊ10 and an oligomeric sulfonium cation compound. As a result, in addition to the chemical formula <[> and <π>, the mixture of the present invention uniquely contains a compound of a di- and/or tri-monomer unit' And any other oligomeric porphyrin cation compound contained in the mixture also has two and/or three monomer units. In this case, other oligo-phenanthride cation compounds may also have a small chemical formula. As a result, the mixture of the present invention not only uniquely contains a compound having the di- and/or tri-monomer unit, but also has other oligomeric porphyrin cation compounds, the other oligo-glycol cation compound The characteristic is an oligomer having an oligomerization degree of 4 or more. More particularly, these other compounds may have the chemical formula <1> and <<>>;11> The substitution form shown in Table 5. The structural unit iskrw'/^ccxr4/474'1)^!^373") is here by the following chemical formulas <1113> and <1111)> Indicates:

R5/575"r4/4'/4" or 10 15 \丫^^/^:|/^^R3/373.. &5/575'1 f^4/474n in chemical formula <1> With <11>, R1, R2, R3, R4, R6, R7, R8, R9 ' R1, R2, R3, R4, R6, R7', R8, R9, R1', R2", R3", R4&quot ; R6", R7", R8' and R9" each independently represent the following: hydrogen, halogen, amine group, wherein the amine group may be more specifically unsubstituted or substituted with a lower alkyl group, further OH, CN, SCN, SH, COOH, COO salt, COO ester, S03H and so3 salt, so3 ester, lower alkyl, wherein the alkyl group may also be substituted, further aryl and heteroaryl. These groups may also be a single bond that groups the individual monomer units together. For the cross-linking of individual monomer units, the mixture of the invention is in a 15 20 1313679 copper coin bath. The utility is not very important, it is, ~,, r4,, r6,, r7,, r8, R9', R1, R2, r3", r4' r6, r7", R8" and R9" Each group can represent the same one . The two outer monomer units in the trimeric compound may be bonded to the same or different C6-rings of the central monomer unit. R5, R5 and R5 are respectively represented as Rl R2, R3, R4, R6 'R' R8, r9, Rl,, r2', r3, r4, R6, r7, r7"r8" and r9" 0, but with the proviso that they are not a single bond. This means that each of the two or two monomer units of the oligomeric phenanthrene compound can be bonded to each other through each carbon atom of the backbone. Monomer unit. However, it is impossible to bond through one of the nitrogen atoms. Further, R2, R2, R2", 3' and r3" are selected from the group consisting of 15 oxy, imine or armor. a group of groups, provided that, in the case of a monomer unit substituted by an oxy group, an imido group or a methyl group, it has a structural unit of the general formula <IIIb> CC (R_C(R·"). This means that in this case, a gambling system is formed in the ring, and an oxy group, an imido group or a methyl group is also bonded thereto. In this paper, it is further considered that various monomer units exhibit mirror symmetry, so in addition to R2, R2', R2", R3' and R3", the R7, R7., R7, R8, R8 and R8 Group can An oxy group, an imido group and a methyl group, since these latter groups can be exchanged with the preceding groups. Among the oligomeric sulfonium cation compounds containing three monomer units, the oxy group, the imine group 16 1313679 and Methyl, preferably bonded to the outer two polymer units. If R2, R2', R2", R3' and R3" are not oxy, imine or methyl, the structural unit NCC ^R1/1 V1")C(R2/272") further has one of the following chemical formulas <IVa> or <1乂1)>: R1/171" /N^A^272. <IVa> Η 卩1/1V1" <!Vb> 5 In the chemical formulas <1> and <11>, A_ is an acidic anion. It is to be noted that A_ may be One having a negative or more negative valence. The molar ratio of the positron to the A-ion is of course dependent on the relative valence. According to the invention, the chemical formula <1> The content of all oligomeric 10 cation cation compounds with <11> is at least 80 mol-% in the mixture. According to DE-AS 20398311, in the conventional two-stage production mode (diazo And in the subsequent formation of the oligomeric phenanthrene cation compound to prepare a known polymer compound, the resulting composition is often a large 15 different and characterized by a different degree of polymerization, with the result that these materials have an electrolyte in the electrolyte. Different effects. Furthermore, for high molecular weight polymeric sulfonium cation compounds characterized by a polymerization degree exceeding 5 17 1313679, the solubility in the copper electrolyte does not perform well, so here they are only allowed in a very limited manner Let it work. The mixtures according to the invention can not be prepared using the process known from DE-AS 2039831. Therefore, the novel synthetic method, in the field of saffron additives, will go beyond the conventional methods to constitute a decisive improvement. Thus, the oligomeric porphyrin cation compound is formed by diazotization of a mixture of one of saffron or several saffron, and by reacting the resulting diazonium compound 10 in a one-pot reaction. These mixtures of oligomeric porphyrin cation compounds obtained are, in particular, the main body of the invention. The novel one-pot reaction allows for the obtaining of a mixture containing predominantly dimeric or trimeric sulfonium cations, and most of which do not contain a polymeric structure. 15 In addition, such oligophenazine cation compounds have been found to contribute to the inclusion of dimers or trimers (when the positive valence is insufficient), so these dimers or Part of the trimer is individually monovalent or divalent. Furthermore, these dimers or trimers have been found to be beneficial for the halogenated sulfonium cation compounds contained in the 20 mixtures of the present invention. They exhibit much higher activity than halogenated monomers or polymers (characterized at a higher degree of polymerization). It can be seen from the examples that the purely halogenated polymeric saffron dye often exhibits poor plating activity. 18 1313679 Further, for those additives exhibiting an increased plating activity, the dimers or trimers (having different monomer units) contained therein are produced by co-dimerization of different saffron dyes or The co-three polymerization or partial decomposition of the above compound occurs during the reaction, and wherein 5 of the oligomeric porphyrin cation compound is formed from the diazotized compound. When using the mixture of the present invention in an acidic electrolytic copper plating bath, it is possible to operate the plating bath below a high current density. In addition, when combined with other conventional additives, it is possible to form a uniform, bright copper deposit. Further, the effect of the oligophenazine cation dye is greatly enhanced by the synthesis according to the present invention. # Adding a special mixture of the oligomeric porphyrin cation compound of the present invention to a copper electrolyte at a lower concentration than the conventional monomeric or polyfluorene cation cation compound used The remarkable luster was then given 15 points. This result allows for better results and benefits. Progressively, the solubility of the 5H-poly or trimeric additive is surprisingly superior to the poly-complexed cation compound. Moreover, in the presence of a catalyst, the synthesis is substantially simplified by the one-pot reaction. 20 Particularly preferred compounds contained in the mixture of the present invention, selected from the group consisting of R'R2, R2", r3, r3.r3", r7 r7, r7 „ R ' R8 and R8 At least one of the eight has a meaning from one of the groups consisting of dentate and meridine. According to a particularly preferred embodiment of the invention, in the trimeric sulfonium 19 1313679 cation compound The base group and the south group are bonded to the positions on the outer two monomer units which are designed to be substituted, and therefore, are selected from the oligomeric fluorene compound according to the chemical formula <::> At least one of the groups comprising a group consisting of r2, r3, R 〃, and R has a 5-member selected from the group consisting of a group consisting of _ 素 and a hydroxy group. It is characterized by the fact that, in the range where they are converted to the lowest current density, a significant gloss is still successfully produced on the deposit. Preferably, among the mixtures, selected from the group consisting of R2, R2, and R. The group's group is such that at least one of the groups represents a lower alkane group, more specifically a methyl group. Ethyl. Such a compound is easily obtained by synthesis. Further, preferably, a mixture of such a type, wherein at least one of the groups consisting of a group consisting of R7 'R7 and R7'' is selected Representing a monoalkylated amine group, more particularly, the amine group is 15 mono- or di-substituted to a lower alkyl group, and more preferably, N-methylamine, N-ethylamine, N,N-di Methylamine and N,N-diethylamine. The use of such a porphyrin cation compound in the inventive mixture, the advantage of an extremely high plating efficiency is achieved. Further advantages of using a mixture, wherein selected from - 20 At least one of the groups of the group consisting of r5'r5' and R5" represents a methyl group or an aryl group. More particularly, the aryl group is a phenyl group or a tolyl group. This mixture 'has the advantage of producing the best results even at the lowest dose in the copper electrolyte', so this deposition method is very useful. 20 1313679 Thereby, the aryl group exhibits an improved plating effect more clearly than the alkyl group. It has been found to be advantageous to use a mixture wherein the acidic anion is selected from the group consisting of sulfuric acid, hydrogen sulphate, sulphuric acid, tetrafluoroboric acid, 5 phosphoric acid, nitric acid, acetic acid, trifluoroacetic acid, and methanesulfonic acid. . It means a family of halogens made of fluorine, gas, desert, and magnetism. Mixtures containing these acidic anions are particularly suitable for use in electrolytic acid copper plating baths because they do not adversely affect the deposition conditions. In addition, dimerized and trimeric sulfonium cation compounds having these acid ions exhibited good solubility in a copper plating bath. In a particularly useful mixture of the present invention, the dimeric and/or trimeric sulfonium cation compound has the following chemical formulas <v>, <VI>, <VII>, and <VIII>:

21 15 1313679 5

In these examples, a divalent oxy group, an amine group or a methyl group is present, so that the electroless stalk is formed in the oligo-phenoline cation compound, which is due to the individual structure. Caused by formation. 10

All R1, r2, r4, r6, r7, r8, R9' R1 in these compounds. ' Rii ' Ri ’ R2', r3', r4, r6, r8, r9, r1. ,

Rl1 ' R1 ' R2' R3'', R4' r6' R8", r9', r1〇„ and r11" may each have a lower one selected from hydrogen containing or such as methyl or ethyl. One of the meanings of the group formed by the institution. A represents a counter anion as previously described, preferably a vapor, a hydrogen hydride or a tetrafluoro acid. The compounds in the mixtures of the invention have the advantage of good uniformity in addition to good brightness. 22 15 1313679 According to the present invention, the following monomer units in the mixture have proven to be particularly effective, and they can still be in both high current density and low current density when they are present in the copper electrolyte at significantly lower concentrations. Excellent brightness is shown: 5 a) 7-N,N-Dimercaptoamino-3-hydroxy-2-methyl-5-phenyl-phenanthridine is shown in the following chemical formula: <a> b) 3-Chloro-7-N,N-dimethylamino-5-phenyl-phenanthridine is shown in the following chemical formula:

<b> c) 8-Dimethylamino-10-phenyl-10hydro-phenant-2-one is shown in the following chemical formula: 23 10 1313679 <c> d) 2-N, N-di The mercaptoamino-10-phenyl-5,10-dihydrophenanthene is shown in the following chemical formula: Η

<d> e) 3-N-Ethylamino-7-hydroxy-5-phenyl-phenophene cation is shown in the following chemical formula:

24 1313679 f) 3-Gas-7-N-ethylamino-5-phenyl-phenanthrium cation is shown in the following chemical formula:

<f>

g) 3-methyl-8-N-methylamino-10-phenyl-10hydro-phenant-2-one is shown in the following chemical formula: <g>

h) 7-N-decylamino-2-mercapto-5-phenyl-5,10-dihydrophenanthene is shown in the following chemical formula: 25 1313679 ΗΝ <h> The following oligomeric porphyrin cations The compounds are detected in the mixtures of the invention and are perfectly suited for electrolytic copper deposition to form combustion at high current densities with a reducing tendency: i. 3'-Ν, Ν-didecylamino-3 ,8'-dimercapto-8-(indolyl-mercaptoamine 5yl)-7'-oxy-10, 5'-diphenyl-5',7'-dioxime-[2,2|] Bis-phenanthryl-10-n-ion-vapor:

Ii. 3,8',8Π-trimethyl-8,3',3Π-gin-(Ν-methylamino)-7"-oxy-10,5',5Π-triphenyl 5", 71,-tetrahydro-[2,2^,21 triple 10 啳-10- positive ion-vaporation: 26

1313679 iii. 8,3,-贰-(N,N-Didecylamino)-8,-methyl-7'-oxy-10,5'-diphenyl-5 dihydro-[2, 2']Diphenazinyl-10-positive ion-hydrogen sulfate:

In the present invention, another substance having very good effect is: iv. 8,8'-贰-(N,N-didecylamino)-3,3'-dimercapto-10,10'-di Phenyl-[2,2']diphenyl-indenyl-10,10'-positive-tetrafluoroborate:

27 <iv> 1313679

v> V v. 8, -贰-(N,N-dimethylamino)-10,10'-diphenyl-3-methyl-[2,2']diphenylen-10 , 10'-positive ion-tetrafluoroborate:

-N vi. 3,8'-贰-(N,N-Didecylamino)-8,3'-dimercapto-5,10,diphenyl5-yl-7-hydroxy-[2,2' Di-linked fluorenyl-5,10'-positive ion-tetrafluoroborate:

Vii. 3,8'-贰-(N,N-Didecylamino)-8,3'-dimethyl-5,10'-diphenyl-7-hydroxy-[2,2']联 嗉 -5-5,10'- cation-chloride:

28 1313679 viii· 3,8,,8”-para-(N,N-didecylamino)-8-methyl-5,10,10′′-triphenyl-[2,2′;7 ',2"]Triple phenanthrene-5,10',10"-positive ion-tetrafluoroborate:

5 ix. 8Ά,Ν-Diethylamino-8-N,Nd-didecylamino-3-methyl-10,10'-diphenyl-[2,2']diphenyl-anthracenyl- 10,10'-positive ion-sulfate:

X. 8'-N,N-Diethylamino-3-N,N-dimethylamino-7-hydroxy-18-10 methyl-5,10'-diphenyl-[2,2 ']Dithiophene-6,10'-positive ion-sulfate: 29

1313679 xi. 8,3',3'-para-(N,N-diethylamino)-7-hydroxy-oxy-10,5,5,-triphenyl-5,10 ,5,,,7,,-tetrahydro-[2,2,,7,,2,,]tripyin 嗔 10 - cation - sulfate nitrogen salt.

Xii. 3,8,贰-(N,N-didecylamino)-7-hydroxy-5,10'-diphenylchun_[2,2']diphenyl--6,10' - cation-sulfate:

30 1313679 xiii. 7-Chloro-3,8'-fluorenyl-(N,N-dimethylamino)-5,10'-diphenyl-8-methyl-[2,2']dithiophene Mercapto-5,10'-positive ion-chlorinated salt:

<xiii> xiv. 7-Chloro-3,8'-fluorene-(N,N-didecylamino)-8,3'-dimethyl-5,10'-5 diphenyl-[2 , 2'] di-indenyl-5,10'-positive ion-vaporized salt:

XV. 7-Gas-3,8'-indole-(N,N-didecylamino)-5,10'-diphenyl-[2,21 dibiphenyl-5,10'-positive Ion-vaporized salt: 31 1313679

Xvi. 7-Gas-3,8',8''-F-(N,N-Dimethylamino)-8,3'-dimethyl-5,10',10',-triphenyl -[2,2';7',2"]Triplexin-5,10',10"-positive ion-vaporized salt:

Xvii. 7-Gas-8, fluorenyl-dimercapto-8'-N,N-dimethylamino-5,10'-diphenyl-[2,2']dibiphenyl-5, 10'-positive ion-chlorinated salt: 32 1313679

Xviii. 8,8'-贰-(N,N-Dimethylamino)-10,10'-dimethyl-[2,2']diphenyl-indenyl-1〇,1〇'- Ion-hydrogen sulfate:

NN . I <XV||i> 5 xix. 8,8,-贰-(Ν,Ν-dimethylamino)-7-oxy-10,5',5"-triphenyl-5 ",7"-dihydro-[2,2';7',2"]tripyin-10,5,-n-ion-hydrogen sulfate:

33 1313679 XX. 8,3',3"- cis-(N,N-diethylamino)-8-mercapto-5,10',10"-triphenyl-[2,2';7 ',2'']Triple phenanthrene-5,10',10"-positive ion-tetrafluoroborate:

5 xxi. 8,8'-贰-(N,N-diethylamino)-10,10'-diphenyl-[2,2']diphenyl-indenyl-1〇,1〇'- Positive ion-tetrafluoroborate:

Xxii. 8,8,-贰-(Ν,Ν-didecylamino)-3-chloro-10,10,-diphenyl-[2,2']dipontyl-10,10' - positive ion - gasification salt:

34 1313679

<xxii> xxiii. 3,3',3"-para-(N-methylamino)-8"-a gas-5,5',5"-triphenyl[8,2';8', 7'']Triple phenotype-5,5',5"-positive ion-vaporized salt:

5 The properties of the dimeric and trimeric phenanthrene cations in the mixture of the invention □ can be confirmed by the following methods: To confirm and quantify the conjugate contained in the mixture according to the invention, the mass spectrometer is Particularly for use in the present case, preferably, the spectroscopy is recorded under the following conditions: by means of electron-jet ionization, the couple is coupled to a 10 quadrupole mass spectrometer (ESI/MS) or a quadrupole ion trap (ESI/QIT- MS), by means of matrix-assisted laser desorption free means, to the quadrupole ion trap (AP-MALDI/Q1T-MS), or by matrix-assisted laser desorption free means to call into the time-of-flight mass spectrometer (MALDI) -TOF). Preferably, the 35 1313679 MALDI method. To quantitatively detect the compound, the sum of all signals in the mass spectrometer was set at 100 mol-%. The detected individual signals correspond to their heights. By this, it is assumed that the ionization degree of the molecular peak assigned by the needle is at the same high level as the sensitivity. Alternatively, the oligomeric sulfonium cation can be quantitatively detected by other methods by a mass spectrometer coupled to a high liquid chromatography unit (LC-MS- Coupling) This is the purpose of assigning individual peaks in HPLC chromatography through a mass spectrometer. After performing a first detection in a reference mixture by means of LC-MS coupling, it can be operated by considering the residence time for the peak of the measurement without LC-MS-coupling. Quantitative determination. Alternatively, the HPLC-method can also be used to quantitatively detect oligomeric phenanthrene cation compounds in the mixture, particularly using gel permeation chromatography. In order to improve the separation of the positively chargeable compound, an anionic 15 wetting agent may be added to the solvent (eluent) of the present invention to form an ion pair (ion pair chromatography). An oligomeric ruthenium cation compound having the structure previously described and included in the mixture of the present invention, which can be diazotized in one sequence, and converted to a chemical formula of < in a one-pot reaction. A single 20-membered cation compound of IX> is obtained by forming the reacted diazonium compound onto the oligophenylene cation compound: 36 1313679

Wherein R1, R2, R4, R5, R6, r7, R8 and ruthenium 9 have the same oligomeric ruthenium cation cation as the previous chemical formula <I> and <11:> The definition given. The term "one-pot reaction" means that the synthesis of the oligomeric porphyrin cation compound $ can be carried out in only a single reactor without removing any intermediates, such as those mentioned. Diazo Compounds. The present invention does not require frustration for the purpose of converting the intermediate product to another reactor without further basic diagnostic inspection, in other words, no drying is required. 1 If the reaction can occur in a single reactor of a suitable size The synthetic hydrazine should still be considered as a one-shot reaction, even though more than one reactor is actually used. Preferably, the reaction is carried out using nitrogen, more particularly nitrogen sulphate or nitrous acid in acid. The base sulfuric acid, preferably an inorganic acid such as fluorophosphoric acid, iodic acid or oxygen desert k, is preferably hydrochloric acid, sulfuric acid, tetrahydroacid, and a mixture thereof. For synthesis, for example, such a red color is preferred. Dyes to be used, which are independent of the R9 system Representing hydrogen, R5 represents a phenyl group, and R7 represents nrWr11, wherein R10 and R11 are each independently 20 having the aforementioned formulas for the chemical formulas <V>, <VI>, <乂11> and <^111>中 37 1313679 One of the definitions given by the same group, more particularly hydrogen and lower grades. The oligomeric porphyrin cation compound in the mixture of the invention may also be used in a one-pot process as described above a different 5-monomer ruthenium cation compound in the chemical formula dX>. Thereby, the diazotized salt can be reacted in situ to the oligomeric porphyrin cation compound, and the reaction can be carried out in a suitable catalyst In the presence of, for example, an alkali metal xanthate, an alkali metal thiocyanate, and an alkali metal selenocyanate, and all of the above transition metals and their 25 compounds are present, 25 Compounds such as elemental copper and its compounds, such as copper (I)- and copper (yttrium)-halides, copper oxide and related copper-based compounds, nickel, ruthenium and iron. The catalyst is preferably in powder form. The original method of the invention is a steel In which the sodium nitrite 15 or nitrosylsulfuric acid is slowly added to the dye which is dispersed in the inorganic acid, under the catalyst of "there" or "none", at a higher temperature 'better' The ground is at a temperature of at least 15 ° C, and especially at 30-60. (:, therefore, the subsequent diazotization by separate, followed by the reaction to form the oligo-phenoxy cation compound is not carried out. 20 After the reaction has been terminated, the reaction product is preferably introduced to The sodium hydroxide test or the potassium-containing test solution 'or is placed in a sulfuric acid concentration of less than 1% by weight' and the resulting solid is filtered out. 1313679 The method of preparation according to the present invention will be carried out as follows EXAMPLES Explanation: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation Example 1: 5 1 g of 3-amino-7-N,N-dimethylamino-2-methyl-5-phenyl-phene The ionic chloride and 174 mg of copper powder were dispersed in 15 m of 50% by weight of tetrafluoroboric acid and heated to 65 ° C. Subsequently, a saturated aqueous sodium nitrite solution (570 mg dissolved) 10 ml of water) was slowly added dropwise, and then mixed at this temperature for another half an hour. 10 The reaction product was cooled to room temperature, and the reaction mixture was introduced into a 50% by weight sodium arsenate lye. The obtained black solid was filtered off and dried. Yield: 520 mg of oligomeric fluorene Positive ion compound 1, which is composed of the following: 15 • 8,8'-贰-(Ν,Ν·dimethylamino)·3,3'-dimethyl.1〇, about a molar percentage 1〇1_diphenyldibiphenyl-methane, ιο'-positive ion tetrafluoroborate (compound <iv>), • 3,8',8"-parameters of about 3 〇% (N,N-dimethylamino group>8-methyl-5,10,,10"_三笨基-(6)义^三联”20 _5,1〇',1〇”' cation-four Fluoroborate (compound <^>), • approximately 15 mole percent of 3, _n, n dimethylamino _38, _ monomethyl-8-(N-methylaminooxy _ 1〇,5,_diphenyl 39 1313679 _5,7-one mouse-[2,2 ]-bipheno-α-methyl-10-n-ion-vapor (compound <i>), and • approximately 15 mo 3,8'-贰-(N,N-didecylamino)-8,3'-dimercapto-5,10'-diphenyl-7-hydroxy-[2,2,] Bis-indenyl-5,10'-n-iono-tetra-gasoside (compound <vi>). Preparation 2: 3-amino-7-team^dimethylamino group of 1〇§ 2-methyl-5-phenyl-phenoxide yttrium cation gas and 2.551 g of copper powder were scattered at 1〇〇 Ml, 50% by weight of tetrafluoroboric acid, and heated to 5 ° C. Following 10 'saturated aqueous sodium nitrite solution (4.164 g dissolved in 15 ml of water) was slowly added dropwise, then At this temperature, another small day was added. The reaction product was cooled to room temperature, and the reaction mixture was introduced into a 50% by weight sodium hydroxide lye. The resulting black solid was filtered off and dried. 15 Product® . 9.8 g of oligo-glycol cation compound 2, which consists of: • 30 mol% of 8,8'_贰_(N,N-dimethylamino)_3,3 , _ dimethyl-10,10'-diphenyl _[2,2']dibiphenyl cation-tetrafluoroborate (compound <iv>), 20 · percentage of moles 3,8 ',8"-tridecyl-8,3',3"_para-(N-methylamino)-7"-oxy-1〇,5,,5"-triphenyl-5,, 10,,5",7"_tetra-argon-[2,2';7',2"]triphenyl--10-positron_vapor (compound <ii>), 40 1313679 • 15% molar percentage 3,_n,N-didecylamino-3 3,8,-dimethyl-8-(N-decylamino)_7'-oxy-1〇,5,-diphenyl_5, , 7'-dihydro-[2,2']diphenyl sulfonyl _10_ cation chloride (compound <i>), and 5 • 8,15,-贰- (N,N-dimethylamino)-10,10'-diphenyl-3-methyl-[2,2']dibiphenyl-anthracene, ι〇ι_ cation-tetrafluoro Borate (compound 〇 >). The first compound <vi> can be obtained by placing a polydextrin column (placed with helium acid) The gel is infiltrated and separated from the mixture. 10 The purity of the compound <vi> is greater than 90%. Preparation 3: 1.5 g of 3-amino-7-N,N-didecylamino group- 2-methyl-5-phenyl_phenanthridine cation gas, 1.5 g of 3-amino-7-N,N-diethylamino-5-phenyl-phene cation cation and 59 〇mg of copper powder is floated in 100 ml, 50% by weight of sulfuric acid, and heated to 50 ° C. Subsequently, a saturated aqueous sodium nitrite solution (1 226 g dissolved in 1 ml of water) was It was slowly added dropwise, and then further mixed for 1 hour at this temperature. The reaction product was cooled to room temperature, and the reaction mixture was introduced into a 50% by weight sodium hydroxide test solution. 20 The body was filtered off and dried. Yield: 0-8 g of oligo-fluorene cation cation compound 3, which consisted of the following: 41 1313679 • 45-mole percent of 8'-(N,N-dimethyl Amino)-8-N,N-dimethylamino-10,10,-diphenyl-[2,2']diphenyl--10,10'-positive-sulfate (compound <;ix>), • 15% of the percentage of 8,3'-贰-(N N-diethylamino)-8'-methyl-5-oxyl-l,5i-diphenyl-5,,7'-dihydro-[2,2,]diphenylen-10-yl Ion-hydrogen sulfate (compound <out>), • 15 mole percent of 8,3',3"-para-(N,N-dimethylamino)-7"-oxy-1〇 ,5',5"-triphenyl-5,,10,,5",7',-tetrahydro-[,,1];?1,"]triphenyl--10-n-ionium-hydrogen sulfate (Compound 10 <xi>), and • approximately 15 mole percent of 3,8,-贰_(N,N-diethylamino)·7-hydroxy-5,10,-diphenyl _ [2,2,]dithiophene-6,l〇|-positive ion-sulfate (compound <v>^). Therefore, the obtained cation-positive compound of the present invention is added to a copper electrolyte by a gloss agent or a emollient agent alone or in combination, more particularly, in an acid bath of an acid (preferably sulfuric acid). . To allow electrolytic deposition of a copper layer over a workpiece, the latter contacts the cathode with the plating bath. The plating bath contains ketone ions as well as the low-loaded ruthenium cation compound of the present invention. For metal deposition, a current density that is subsequently induced 20 flows between the workpiece and the cathode. The basic composition of the copper electrolyte can be varied over a wide range. In general, an acidic aqueous copper ion containing a solution having the following composition: 42 1313679 Preferably, the copper sulfate hydrate is preferably concentrated sulfuric acid, preferably 0.01-0.25 g/1, preferably 0.05-. 0.14 g/1 In addition to copper sulphate, other copper salts may be used in at least a portion. Sulfuric acid may also be partially or completely substituted with fluoroboric acid, methicillin or other acids. The gas ions may also be added as an alkali metal chloride (e.g., sodium chloride) or as a hydrogen acid in analytical grade purity. If the addition contains _ 素 ions, the added sodium sulphide may be partially or completely dispersed. 0.00005-0.1 One concentration is added to the plating bath 10 20-300 g/1 180-220 g" 50-350 g/1 50-90 g/1 The oligophenazine cation compound of the present invention is excellent in the system The mineral bath may further comprise an existing glossing agent, leveling agent or lubricant. In order to obtain a bright copper deposit exhibiting physical properties, a sulfur-soluble sulfide and an oxide containing a high molecular weight compound may be added to the acid bath of the present invention. Additional additives such as sulfide-containing nitrides and/or polynitrogen compounds may also be used. Immediately available plating baths contain the following concentrated chrome components: "The general oxides in the range of degrees include, 43 15 1313679 high molecular weight compounds 0.005 -20g / l preferably 0.01 -5g / l generally water soluble The organic sulfide is 0.0005-0.4 g/l, preferably 0.001-0.15 g/l. Some oxides having a high molecular weight compound are described as follows: carboxymethylcellulose, nonylphenyl-polyglycol ether, xin Alkanediol-indole (polyglycol ether), octyl polyglycol ether, polyglycol oleate, polyethylene glycol-polypropylene glycol (block or copolymerized product), polyethylene glycol, polyethylene Alcohol 5-dimethyl ether, polypropylene glycol, polyvinyl alcohol, β-phenol polyglycol ether, polyglycolic acid polyglycol ester, stearyl ketone polyglycol ester. Some sulfides are described as follows: 3-( Sodium salt of phenyl thiathiazolyl-2-thio)-propyl sulfonic acid, sodium salt of 3-mercaptopropane-1-sulfonic acid, sodium salt of ethyl dithiodipropyl sulfonic acid, 贰-( Two 10 nano-salts of ρ-thio-phenyl)-disulfide, di-sodium salt of i-(c〇-thio-benphin)-disulfide, wu-(c〇-thio-butyl)- Disulfide disodium salt , 贰-(ω-thiohydroxypropyl)-disulfide disodium salt, C-(〇>-thiopropyl)-disulfide di-sodium salt, 贰-(ω-thio-propionate Di-sodium salt of disulfide, disodium salt of wu-(ω-thiopropyl)-disulfide, 0-ethyl-dithiocarbonate-(ω-thiopropyl)-ester 15 potassium salt, thioglycolic acid, 0-ethyl-indole-(ω-thiopropyl)-ester disodium salt and thiolated acid-para-(ω-thio-propyl)- Salts. Related functional groups have been incorporated for water solubility. Nitrogen containing sulfides, more particularly sulfur containing nitrides, 44 1313679 preferably thiourea derivatives and/or polynitrogen Compounds such as polyamines and polyamines can be used in the following concentrations: 0.0001 - 0.50 g/1

Preferably, it is 0.0005 - 0·04 gA. Preferred sulfur-containing nitride is described as follows: N-acetylthiourea, N-ethylidene sulfide, N-ethylthiourea, N-cyanide Ethyl thiol 5 thiourea, N-allyl thiourea, hydrazine- phenyl thiourea, N, N'-butyl thiourea, thiazolidine thiol (2), 4-thiazoline thiol ( 2) Imidazoline thiol (2) (N; N'_ethyl thiourea), 4-methyl-2-pyrimidinyl mercaptan, 2-thiourea pyridine, sodium salt of saccharin. Preferred polynitrogen compounds are exemplified in the following: polyethyleneimine, polyethylenimine, polyacrylamide, polypropyleneimine, polybuteneimide, fluorene-methylpolyethyleneimine, Ν-Ethylene-based polyethyleneimine, hydrazine-butylpolyethyleneimide. To prepare the plating bath, individual ingredients are added to the base composition. The operating conditions of the plating bath can be more specifically set as follows: 15 pH: <1

Temperature: 15 ° C - 50 ° C, preferably 20 ° C - 40 ° C Cathode current density 0.5-12 A / dm 2 , preferably 3-7 A / dm 2 electrolyte can be stirred through a strong fluid flow It is also possible to inject clean air, thereby subjecting the surface layer of the electrolyte to 20 strong agitation. This is done to maximize the conversion of the material closest to the electrode and to allow for a higher current density. The movement of the cathode also promotes the conversion of the substance throughout the surface layer. Convection and shifting by the electrodes 45 1313679 The system is allowed to achieve continuous, diffusion-controlled deposition. Movement can be caused either horizontally or vertically and/or by vibration. Combinations with air injection are particularly effective. In order to keep the copper content constant, the copper 5 can be electrically replenished by decomposing the copper electrode. The copper used for the anode may be a copper containing phosphorus (〇2 to 0_07%) enclosed in a filter bag. It is also possible to use an anode made of titanium or other plating. In the production line of the prior art, when working on the line, the workpiece is coated in a vertical or horizontal direction. 10 If necessary, a filter to contain mechanical and/or chemical residues can be placed in the electrolysis cycle. The copper electrolyte of the present invention is perfectly suited for the manufacture of a decorative deposit. It can be further used in blind micropores that are electrolytically filled in the printed circuit board. This constitutes a future-oriented technology that allows wafer makers to be particularly concerned with thin film circuit traces, and the increased reliability can be achieved using copper sleeve technology. Under a similar method, the copper electrolyte of the present invention provides a concise and definitive solution for generating a semiconductor substrate (grooves and holes) provided by the circuit during the fabrication of the integrated circuit. Round) on the surface. The layer of the copper ore which is almost constant and has a thickness of 3 〇 (planar) is obtained on the entire surface of the wafer, and the individual grooves have a high aspect ratio (1:1 〇). Thus, the grooves (blind micro holes) such as these are filled with copper. The present invention will be further understood by studying the following method examples and the accompanying drawings, which illustrate: Figure 1. shows a copper plated process according to Method Example 6 (without the use of the blend 46 1313679 compound of the present invention) A cross section of a blind hole in a printed circuit board; Fig. 2: shows a cross section of a blind hole in a printed circuit board after copper plating according to method embodiment 7 (using the mixture of the invention). Method Example 1 (Comparative Test): 5 In a cell having a soluble, copper-containing anode phosphorus, a copper bath having the following composition was used: 200 g/Ι copper sulfate pentahydrate (CuS04 · 5H20) 6〇g/Ι concentrated sulfuric acid. 0.12 gM vaporized sodium 10 The following brighteners were added: 1·5 g/Ι Polypropylene glycol (800 Da (dalton)), 0·006 g/1 3 - Sodium decylpropane-1.sodium sulfonate salt at a temperature of 25 ° C and a current density of 4 A / dm 2 , a uniform, bright, slightly sloppy deposit on a brush 15 brass sheet obtain. Method Example 2 (Comparative Test): According to Method Example 1, 5 mg/1 of 7-dimethylamino-3-poly-5-phenyl-phene-anthracene chloride (according to jp 6〇_〇) 56 〇 86 a, which was prepared by the singer, was further added to the electrolyte. When, copper, was deposited under the conditions shown in Method Example 1, the copper layer obtained had a slightly improved appearance. In the present embodiment, the brass sheet has an appearance of a lighter shell but exhibits a burnt shape at the edges, which occurs here due to a high current density. Method Example 3 (comparative test): 25 5 mg/l poly-(7-dimethylamino-5-phenyl-phenazine cation) sulphur 47 1313679 acid ester [having an average of about 8000 Da Mohility] was further added to the electrolyte according to Method Example 1. The resulting compound is similar to that described in DE-AS 2039831, 7th, 2nd, and the foregoing. When "copper" was deposited under the conditions shown in the method example 1, the copper deposit obtained on a brushed brass sheet was of good quality. The deposit exhibited consistent brightness without charring. The brush line is almost invisible. This means that the copper electrolyte has a certain homogenization effect. Method Example 4: 4 mgA of the present invention <iii>, <vi>, <xi> and <xii> a mixture of dimeric or 10-trimeric compounds [having a large approximately 8000 Da (627-913 Da) The average molar weight of the substrate was further added to the electrolyte according to Method Example 1. When "copper" was deposited under the conditions shown in Method Example 1, the copper deposit obtained on a brushed brass sheet had a very good appearance. The deposit exhibited high brightness without charring. 15 The brush line is now completely invisible. This indicates that the copper electrolyte has an excellent homogenization effect. Method Example 5: a mixture of the present invention <xiii>, <xiv>, <xv>, <xvi> and <xvii> dimerization or trimerization of only 3 mg/1 [having one An average molar weight of about 20 8000 Da (627-913 Da) was further added to the electrolyte according to Method Example 1. When "copper" was deposited under the conditions shown in the method example 1, the brass sheet had an extremely good appearance. The deposit is extremely bright and mirror-like. The copper sheet showed no charring. The brush line is absolutely invisible. This indicates that the copper electrolyte has an excellent homogenization effect of 25 even though the amount of the mixture has been reduced. 48 1313679 It may be shown by the results of Examples 1 to 5 that the mixture of chlorides containing the monomeric phenazine cation compound has only a low homogenization effect. The polymerized ruthenium cation compound has a good effect. 5 In any case, as shown in Example 4 and Example 5, this utility can be significantly improved when using the dimeric or trimeric mixture of the present invention, in fact, the significantly improved utility is A gas atom is incorporated into the solution. In this case, it is possible to reduce the concentration considerably, but still obtain excellent results. 10 Method Example 6 (Comparative Test): When plating a printed circuit board having blind micropores, a copper plating bath having the following composition was used in an electrolytic cell having a soluble copper anode containing phosphorus. : 150 g/Ι Copper sulfate pentahydrate (CuS04 _ 5H20) 15 200 g/1 Concentrated sulfuric acid 0.05 g/1 Sodium vapor The following brighteners are added: 0.5 g/Ι Polypropylene glycol (820 Da ( Dalton)), 0.005 g/1 贰-(ω-thiopropyl)-disulfide disodium salt 20 at a temperature of 25 ° C and a current density of 1 A/dm 2 The deposit was obtained after a 114 minute exposure time on a 8 μιη printed circuit board with small blind vias (blind microvias) with a width of 110 μm and a depth of 60 μm and almost no Filled with copper. Figure 1 shows the cross section of the blind hole. Method Example 7: 49 25 1313679 4 mgd of the present invention <iii>, <vi>, <xi> and <xii> a mixture of dimeric or trimeric compounds [having a large approximately 8000 Da (627- The average molar weight of 913 Da) was further added to the electrolyte according to Example 6. When "copper" was deposited under the conditions shown in Method Example 6, the appearance on the printed circuit board was improved. A blind hole system having a width of 110 μm and a depth of 60 μm is completely and selectively filled with copper. After the copper plating operation, no grooves are seen. It is low in terms of the total amount of copper deposited. Figure 2 shows a polished cross section of such a copper plated blind hole. 10 This result is a significant improvement over the electrolytic copper keys for blind holes known in the prior art, as these blind holes can be filled in a better manner. This rationale is to substantially improve the homogenization effect of the copper plating bath (obtained from the mixture of the oligomeric porphyrin cation compounds of the present invention). Furthermore, the reliability of the copper deposited on the wall of a blind hole and the copper layer blocked by the 15 hole is better than that of the conventional copper plating technique. Moreover, when the mixture according to the invention is used, no separation layer is detected between the two metal layers during the hot solder impact test, however, when a known mixture is used under these conditions, such a The danger of separation. It should be understood that the embodiments and specific examples described herein are for illustrative purposes only, and that various modifications may be made by those skilled in the And variations are intended to be included within the spirit and scope of the invention and the scope of the appended claims. All of the publications, patents and 25 patent applications cited herein are incorporated herein by reference. 50 1313679 [Simple description of the drawing 3 FIG. 1 : shows a cross section of a blind hole in a printed circuit board after copper plating according to method embodiment 6 (the mixture of the invention is not used); FIG. 2 : shows a method according to the method Example 7 (using the hybrid 5 of the present invention) was used to perform a cross section of a blind hole in a printed circuit board after copper plating. [The main components of the diagram represent the symbol table]

51

Claims (1)

1313679- Patent application No. 92135371 Patent application scope amendment 98.03.23 Announcement, the scope of patent application: (four) month 》 〉 day revision 1. A mixture of oligomeric phenanthrene cation compounds, which contains at least one choice From the cation cation compound contained in the following group: a) a compound 5 containing a dimer monomer unit having the following chemical formula &lt;1&gt;: (A·> (A-) and b) a compound containing a tri-monomer having the following chemical formula &lt;II&gt;: 10 (Α·) (Α') with a further oligomeric phenanthrene cation compound, wherein, in the above chemical formulas &lt;1&gt; and &lt;11&gt;, structural unit n(r5/5V5&quot;)cc(r4 /4'/4I')c(r3/3V3&quot;) has one of the following chemical formulas &lt;1113&gt; or &lt;11113&gt;: N ^ 丫\r3/373' r5/5V5m R4/4V4'' 52 15 1313679 (j^5/575&quot; p4/4V4M where R1, R2, R3, R4, R6, R7, R8, R9, R1', R2', R3', R4, R6', R7', R8 , R9', R1', R2, R3", R4', R6', R7, R8, '5 and R9&quot; each have a meaning selected from the group consisting of: hydrogen, halogen , amine, OH, CN, SCN, SH, COOH, COCT metal salts, soil test metal salts, salt and copper salts, carboxylic acid esters of Ci to c8 alcohols, alkali metal salts of S03H and so3_, alkaline earth a metal salt, an aluminum salt, and a copper salt, (^ to a heart alcohol sulfate, (^ to (8 alkyl, benzene 10 and polycyclic aromatic and pyridyl, quinolyl, isoindolinyl, and one) A single bond that links individual monomer units together, R5, R5' and R5&quot; Each is the same as R1, R2, R3, R4, R6, R7, R8, R9, R1', R2', R3', R4', R6', R7_, R8', R9', Rr, R2_', R3" , R4&quot;, R6'', R7", R8&quot; and R9'', but there are 15 pieces that do not represent a single bond, R2, R2', R2&quot;, R3' and R3&quot; may additionally be selected from The group consisting of an oxy group, an imido group and a fluorenyl group, provided that a monomer unit substituted by a pendant oxy group, an imido group or a methyl group contains a chemical formula &lt;IIIb&gt; Structural unit N(R5/5V5")CC(R4/4V4&quot;)C(R3/3W), 20 wherein, further, if R2, R2', R2'1, R3' and R3'1 are not side In the case of an oxy group, an imido group or a methyl group, the structural unit Να:(Κ1/ινι&quot;)(:(Ι^'/2'') 53 1313679 has the following chemical formula &lt;8^&gt; or &lt; One of 1¥13&gt;: &lt;IV a&gt; H pi / r / r &lt; IV b &gt; γ γ ^ 2 / 2 '/2 &quot; wherein, further, A - is an acidic anion, and Further, all of the oligophenazines having the chemical formulas &lt;1&gt; and &lt;11&gt; The ionic compound is contained in the mixture in an amount of at least about 80 mol-%, wherein is selected from the group consisting of R2, R2', R2", R3, R3', R3', R7, R7' At least one of the residues of the group of R7&quot;, R8, R8' and R8'' has one meaning selected from the group consisting of halogen and hydroxyl groups. 10. A mixture of oligo-fluorene ruthenium cation compounds according to claim 1 wherein the oligo-phenylene compound according to the chemical formula &lt;11&gt; is selected from the group consisting of R2, R3, R7&quot; and R8_' At least one of the residues of the group has a meaning selected from the group consisting of a halogen and a hydroxyl group. 3. A mixture of oligo-fluorene cation compounds according to claim 1 wherein at least one of the residues selected from the group consisting of R2, R2' and R2'- represents (^ to (8 alkyl). Γ Γ. 1 L -J·. -i 54 1313679 4. A mixture of oligophenazine cation compounds as in claim 3, wherein the heart to the alkane The base is a thiol group or an ethyl group. 5. A mixture of oligo-fluorene sulfonium cation compounds according to claim 1 wherein the residue is selected from the group consisting of R7, R7' and R7&quot; At least one of the groups 5 represents an alkylated amine. 6. A mixture of oligo-phenoxy cation compounds according to claim 5, wherein the alkylated amine is selected from the group consisting of N a group of methylamine, N-ethylamine, hydrazine, hydrazine-diamine and hydrazine, hydrazine-diethylamine. 7. A mixture of oligo-fluorene cations of the ionic compound of claim 1 Wherein at least one of the residues selected from the group consisting of R5, R5' and R5&quot; represents a thiol or an aryl group. A mixture of oligomeric ruthenium cation compounds of item 7, wherein the aryl group is phenyl or fluorenyl phenyl. 9. Mix of oligo-fluorene ruthenium cation compounds as in claim 1 And wherein the acidic anion Α is selected from the group comprising: sulfuric acid, hydrogen sulphate, halide, tetrafluoroboric acid, hexafluorophosphoric acid, nitric acid, acetic acid, trifluoroacetic acid, and hydrazine sulfonic acid. A mixture of oligo-fluorene ruthenium cation compounds of claim 1 wherein the monomer unit in the compound is selected from the group consisting of the following 20 groups: (a) 7-oxime, Ν-dimethylamine 3-hydroxy-2-methyl-5-phenyl-phenanthridine cation (b) 3-chloro-7-indole, fluorenyl-dimethylamino-5-phenyl-phenanthridine cation (c 8-Dimethylamino-10-phenyl-10hydro-phenanth-2-one 55 1313679 (d) 2-indole, fluorenyl-dimethylamino-10-phenyl-5,10-di (e) 3-N-ethylamino-7-hydroxy-5-phenyl-phenanthridine (f) 3-chloro-7-N-ethylamino-5-phenyl-phen Ruthenium ion (g) 3-methyl-8-N-methylamino-10-phenyl-10-hydro-phenanth-2-one (h) 7-N-methylamino-2-methyl -5- A mixture of oligomeric ruthenium cation compounds according to claim 1 wherein the mixture is at least one of the following chemical formulas &lt;I X&gt; The body is prepared by diazotization of a positive ion compound: &lt;IX&gt; wherein R1, R2, R4, R5, 豕6, R7, R8 and R9 have the same definitions as given in the previous 10, and the diazotized compound obtained by the reaction in a one-pot reaction The oligomeric phenanthrene cation compound is formed. 12. A mixture of oligomeric phenanthrene cation compounds as claimed in claim 1 wherein the compounds have the following chemical formulas selected from the group consisting of: b &lt;V&gt; 56 U13679 has the meaning of 及 and its R1〇, RU, R1〇, 尺川, Rl〇 and R11&quot; are hydrogen or (^ to (: 8 alkyl). a mixture of oligophene A cation compounds according to claim 1 of the patent (4), wherein they are selected from the group consisting of: l' 3'-N,N-dimethylamino group _3, 8'-Dimethyl-8-(N-methylamino)-7- pendantoxy-10,5,-diphenyl-5',7,-dihydro-[2,2']嗉基-10·正离子-化化Η·3,8',8&quot;-trimethyl-8,3',3&quot;·gin-(Ν-methylamino)-7&quot;-sideoxy -1〇,5',5"·triphenyl-5',10',5",7"-tetrahydro-[2,2,;7,2"]triphenyl--10-positron- Chloride iii. 8,3'-贰-(Ν,Ν-dimethylamino)-8'-methyl-7'-sideoxy-10,5'- 57 15 1313679 diphenyl-5' , 7'-dihydro-[2,2']diphenyl--10-n-ionium-hydrogen sulfate^8,8'-贰-(condition dimethylamino)-3,3'- Dimethyl-10,10'-diphenyl-[2,2']dipontyl-10,10'-positive-tetrafluoroborate 5 v. 8,8'-贰-(Ν, Ν-Dimethylamino)-10,10'-diphenyl-3-methyl-[2,2,]diphenyl-indenyl-10,10'-positive-tetrafluoroborate vi. 3 ,8'-贰-(Ν,Ν-didecylamino)-8,3'-dimethyl-5,10'-diphenyl -7-7-hydroxy-[2,2']dibiphenyl--5,10'-n-ion-tetrafluoroborate 乂 is 3,8 匕贰-(fan dimethylamino)-8, 3'-Dimethyl-5,10'-diphenyl 10 -7-hydroxy-[2,2']dipontazine-5,10'-positron-chloride 乂.3,8' , 8"- gin-(fanyi-didecylamino)-8-methyl-5,10',10&quot;-triphenyl-[2,2';7',2"]triphenyl-5 ,10,,10&quot;-positive ion-tetrafluoroborate ix. 8'-Ν, Ν-diethylamino-8-oxime, Ν-dimethylamino-3-methyl 15- 10,10 '-Diphenyl-[2,2']diphenyl-indenyl-10,10'-positive ion-sulfate X. 8'-where: ^-diethylamino-3-van: ^-two Mercaptoamino-7-hydroxy-8-mercapto-5,10'-diphenyl-[2,2']dibiphenyl--6,10'-positive-sulfate 20 xi. 3',3"-para-(N,N-didecylamino)-7&quot;-sideoxy-10,5',5"-triphenyl-51,10',5",7"- Tetrahydro-[2,2,;7',2,,]tripyin-10-n-ionium-hydrogen sulfate xii. 3,8'-贰-(N,N-diethylamino)-7 -hydroxy-5,10'-diphenyl-[2,2']dibiphenyl--6,10'-positive-sulfate 58 1313679 forked out.7-chloro-3, 8'-贰-(Fan Dimethylamino)-5,10'-diphenyl-8-methyl-[2,2']diphenyl-indenyl-5,10'-n-ion-chloride Xiv. 7-Chloro-3,8'-贰-(Ν,Ν-dimethylamino)-8,3'-dimethyl-5,10'-diphenyl-[2,2'] Di-indenyl-5,10'-positronium-chloride 5 XV. 7-chloro-3,8'-fluorene-(fluorene, fluorenyl-didecylamino)-5,10'-diphenyl -[2,2'] Di-indenyl-5,10'-positive-rat compound xvi. 7-Chloro-3,8',8"-para-(Ν,Ν-dimethylamino) -8,3·-dimethyl-5,10,,10''-trimethyl-[2,2';7',2,']triphenyl-indenyl-5,10',10&quot;-positive Ion-chloride 10 Fork 7-chloro-8,1'-dimethyl-8'-team!^Dimethylamino-5,10'-diphenyl-[2,2']嗉-5,10'- cation-chloride xviii. 8,8'-贰-(N,N-didecylamino)-10,10'-dimethyl-[2,2'] Diphenophene β-methyl-10,10'-positive ion-hydrogen sulfate xix. 8,3,,3&quot;-para-(Ν,Ν-dimethylamino)-7"-sideoxy-10 ,5,,5"- 15 triphenyl-5",7"-dihydro-[2,2';7',2"]tripyin-10,5'-positive ion-hydrogen sulfate XX. 8,3,,3"-parameter-(team 沁dimethylamino)-8-methyl-5,10 , 10"-triphenyl-[2,2,;7,,2"]tripyin-5,1〇|,10"-positronium-tetrafluoroborate 20 xxi. 8,8'-贰- (N,N-didecylamino)-10,10'-diphenyl-[2,2']dibiphenyl-indenyl-1,1〇'-positive-tetrafluoroborate xxii. 8 , 8'-贰-(N-methylamino)-chloro-10,10,-diphenyl-[2,2']diphenyl-indenyl-1,1〇'-positive-chloride Xxiii. 3,3',3"-para-(N-methylamino)-8"-chloro-5,5·,5"-triphenyl 59 1313679 _[8,2';8',7" ]-Triple-anthracene-5,5',5"-positive ion-vapor. 14. A method for preparing a mixture of oligophene β-Qin cation compounds as claimed in claim 1, wherein at least one monomeric ruthenium cation compound having the following chemical formula &lt;ΙΧ&gt; Diazotization, The definition; and the diazonium compound formed in the diazonium reaction is reacted into a mixture of the oligophene 51 Qin cation compound in the _ steel reaction. 10 I5. The method of claim 14, wherein the monomeric cation cation compound having the chemical formula &lt;ιχ&gt; is selected from the group consisting of saffron dyes, wherein R1, R4, V and R9 Each of them represents money, Han 5 represents a phenyl group and R7 represents NRY, wherein R1〇 and Rn each independently have one of the aforementioned meanings. ' 15 I6. The method of claim 14 or 15, wherein: a) the mixture of saffron or saffron is dispersed in the mineral acid bismuth and b) at - at least the temperature of the hearing, Nitric acid or nitrososulfuric acid is added to the dispersion of the saffron or saffron mixture placed in the mineral acid. The method of claim </ RTI> wherein the inorganic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, tetrafluoroboric acid, hexafluorophosphoric acid, 60 1313679 phosphoric acid, hydrobromic acid, and mixtures thereof . 18. The method of claim 14 or 15, wherein the diazonium compound obtained is reacted in the presence of a catalyst to form a mixture of the oligomeric porphyrin cation compound selected from the group consisting of a metal comprising a group of 5 copper, nickel, palladium, and iron or a compound of these metals, or selected from the group consisting of a metal-containing xanthogenate, a metal thiocyanate, and a metal selenocyanate. The group consists of compounds. 19. The method of claim 18, wherein the metal compound is selected from the group consisting of oxides, imides and pseudohalides of metals. 10. The method of claim 18, wherein the catalyst is in the form of a powder. An acid bath for electrolytically depositing a copper deposit, the acid bath comprising an oligomeric phenanthrene cation compound, wherein the oligo-anthracene cation compound is in the form of a mixture as claimed in claim 1 Is included. An acid bath according to claim 21, wherein the mixture of the oligomeric porphyrin cation compounds is contained at a concentration of 0.00005-0.1 g/Ι. 23. The acid bath of claim 21 or 22 additionally comprising a compound selected from the group consisting of nitrogen-containing sulfur compounds and polymeric nitrogen compounds. 20. The acid bath of claim 23, wherein the concentration of the nitrogen-containing sulfur compound and the polymerizable nitrogen compound contained in the acid bath is 0.0001 - 0.50 g / Torr. 25. A method for electrolytically depositing a copper deposit by which a working member is contacted with an anode and a plating bath containing copper ions and a mixture of the scope of the patent application No. 1 61 1313679 Current flow is generated between the workpiece and the anode. 26. Use of the method of claim 25, for depositing a highly bright, uniform 5 copper deposit for the purpose of creating a decorative surface. 27. Use of the method of claim 25, for forming a copper deposit on a printed circuit board having blind microvias. 28. Use of the method of claim 25, for forming a copper deposit on a semiconductor substrate having a high aspect ratio groove. 10 62